JP3837573B2 - Method for producing carbon nanotube bonded with nitrogen atom - Google Patents
Method for producing carbon nanotube bonded with nitrogen atom Download PDFInfo
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- JP3837573B2 JP3837573B2 JP2004081472A JP2004081472A JP3837573B2 JP 3837573 B2 JP3837573 B2 JP 3837573B2 JP 2004081472 A JP2004081472 A JP 2004081472A JP 2004081472 A JP2004081472 A JP 2004081472A JP 3837573 B2 JP3837573 B2 JP 3837573B2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 26
- 239000002041 carbon nanotube Substances 0.000 title claims description 26
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 title description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000619 electron energy-loss spectrum Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- -1 reaction temperature Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
Description
この出願の発明は、窒素原子が結合したカーボンナノチューブの製造方法に関するものである。さらに詳しくは、電界放出特性、ガス貯蔵特性、電子移動特性などに優れている高窒素原子含有率のカーボンナノチューブの製造方法に関するものである。 The invention of this application relates to a method for producing a carbon nanotube having nitrogen atoms bonded thereto. More specifically, the present invention relates to a method for producing a carbon nanotube having a high nitrogen atom content that is excellent in field emission characteristics, gas storage characteristics, electron transfer characteristics, and the like.
従来より、様々な組成および形態のナノチューブが注目されているが、この中でも窒素原子を含有したカーボンナノチューブは、電界放出特性、ガス貯蔵特性、電子移動特性などに優れた特性を示し、電気部品の素材をはじめ、各種分野でその応用が期待できることから、近年多大な関心を集めている。 Conventionally, nanotubes with various compositions and forms have attracted attention. Among them, carbon nanotubes containing nitrogen atoms show excellent characteristics such as field emission characteristics, gas storage characteristics, and electron transfer characteristics. In recent years, it has attracted a great deal of interest because it can be used in various fields including materials.
この窒素原子を含有したカーボンナノチューブは、化学的気相成長法（ＣＶＤ法）で製造されることが知られている。この方法によれば、カーボンナノチューブへの窒素原子の導入率は、原料の種類、触媒、反応温度、ガスの流量などの合成条件が大きく影響する。これまで、このＣＶＤ法に用いる原料として、塩化シアヌル、ピリジン、メラミン、トリアジン、アセトニトリル、フラーレン、メタン、しょうのう、金属フタロシアニン等が使用された例が報告されている。（非特許文献１〜５）
しかしながら、上記方法により製造されたカーボンナノチューブの窒素原子の導入率は低く、たとえば、メタンなどの窒素原子を含まない原料をアンモニアあるいは窒素の存在下で燃焼させた場合には、窒素原子の導入率は高々１０ａｔｏｍ％までである。また、窒素原子を含む原料を用いた場合でも、これまでの窒素原子の導入率は１３ａｔｏｍ％以下であり、電界放出デバイス、ガス貯蔵材料等の各種分野への応用展開を困難にしている。このため、高い窒素原子含有率のカーボンナノチューブの製造方法は、いまだ確立されていないのが実情である。 However, the introduction rate of nitrogen atoms in the carbon nanotubes produced by the above method is low. For example, when a raw material not containing nitrogen atoms such as methane is burned in the presence of ammonia or nitrogen, the introduction rate of nitrogen atoms Is at most 10 atom%. Even when a raw material containing nitrogen atoms is used, the introduction rate of nitrogen atoms so far is 13 atom% or less, which makes it difficult to develop applications in various fields such as field emission devices and gas storage materials. For this reason, the actual situation is that a method for producing a carbon nanotube having a high nitrogen atom content has not yet been established.
そこで、この出願の発明は以上のとおりの背景よりなされたものであって、窒素原子の導入率が１９〜２５ａｔｏｍ％である高い窒素原子含有率のカーボンナノチューブを製造することのできる新しい方法を提供することを課題としている。 Therefore, the invention of this application has been made based on the background as described above, and provides a new method capable of producing a carbon nanotube having a high nitrogen atom content with a nitrogen atom introduction rate of 19 to 25 atom%. The challenge is to do.
この出願の発明は、上記の課題を解決するものとして、第１には、酸化鉄と酸化モリブテンが保持されたアルミナ基板を加熱炉に設置し、この炉中にＮ，Ｎ-ジメチルホルムア
ミド蒸気とアンモニアガスを導入し、５００℃以上の温度で加熱することを特徴とする窒素原子が結合したカーボンナノチューブの製造方法を提供する。
In order to solve the above-mentioned problems, the invention of this application firstly, an alumina substrate holding iron oxide and molybdenum oxide was installed in a heating furnace, and N, N-dimethylformamide vapor and Provided is a method for producing a carbon nanotube having nitrogen atoms bonded thereto, wherein ammonia gas is introduced and heated at a temperature of 500 ° C. or higher.
第２には、アルミナ基板は、シリコンの表面にアルミナ薄膜が配設された基板とすることを特徴とする製造方法を提供する。 Second, there is provided a manufacturing method characterized in that the alumina substrate is a substrate in which an alumina thin film is disposed on a silicon surface.
第３には、６００℃〜９００℃の温度範囲において加熱することを特徴とする製造方法を提供する。 3rdly, the manufacturing method characterized by heating in the temperature range of 600 to 900 degreeC is provided.
上記のとおりこの出願の発明によれば、窒素原子の導入率が１９〜２５ａｔｏｍ％である高い窒素原子含有率のカーボンナノチューブの製造方法が提供される。 As described above, according to the invention of this application, a method for producing a carbon nanotube having a high nitrogen atom content with a nitrogen atom introduction rate of 19 to 25 atom% is provided.
この出願の発明は上記のとおりの特徴をもつものであるが、以下にその実施の形態について説明する。 The invention of this application has the features as described above, and an embodiment thereof will be described below.
まず、この出願の発明が提供する窒素原子が結合したカーボンナノチューブの製造方法は、酸化鉄（Ｆｅ2Ｏ3）と酸化モリブテン（ＭｏＯ3）が保持されたアルミナ（Ａｌ2Ｏ3
）基板が加熱炉に設置され、この炉中にＮ，Ｎ-ジメチルホルムアミド蒸気とアンモニア
ガスを導入し、５００℃以上の温度で加熱することを特徴としている。
First, the method for producing a carbon nanotube bonded with nitrogen atoms provided by the invention of this application is an alumina (Al 2 O 3 ) holding iron oxide (Fe 2 O 3 ) and molybdenum oxide (MoO 3 ).
) The substrate is placed in a heating furnace, and N, N-dimethylformamide vapor and ammonia gas are introduced into the furnace and heated at a temperature of 500 ° C. or higher.
この出願の発明において、アルミナ基板は、シリコン、アルミナ、炭化ケイ素、窒化ケイ素、窒化ホウ素などの基板にアルミナがコーティングされたものであってもよく、特にシリコンの表面にアルミナ薄膜が配設された基板が好ましい。酸化鉄と酸化モリブテンが保持されたアルミナは、たとえばゾル−ゲル法で作製し、高温の処理温度でも安定なシリコン基板上にスピンコートさせて作製したものであってもよい。 In the invention of this application, the alumina substrate may be a substrate of silicon, alumina, silicon carbide, silicon nitride, boron nitride or the like coated with alumina, and in particular, an alumina thin film is disposed on the surface of silicon. A substrate is preferred. The alumina holding iron oxide and molybdenum oxide may be prepared by, for example, a sol-gel method and spin-coated on a silicon substrate that is stable even at a high processing temperature.
そして、上記の基板を加熱炉に配置し、Ｎ，Ｎ-ジメチルホルムアミド内に不活性ガス
を吹き込み、Ｎ，Ｎ-ジメチルホルムアミドを霧状化して炉内に導入する。
Then, the substrate is placed in a heating furnace, an inert gas is blown into N, N-dimethylformamide, and N, N-dimethylformamide is atomized and introduced into the furnace.
加熱炉としては、たとえば、電気炉、マイクロ波加熱炉等の各種のものが挙げられ、横型、縦型のいずれかであってもよいが、操作等が容易であることから、横型石英管状炉が好適に用いられる。 Examples of the heating furnace include various furnaces such as an electric furnace and a microwave heating furnace, which may be either a horizontal type or a vertical type. Are preferably used.
不活性ガスはキャリアガスとしての役割をもち、その流量は１００〜５００ｍｌ／ｍｉｎの範囲が好ましい。不活性ガスの流量が５００ｍｌ／ｍｉｎより多いと、未分解のＮ，Ｎ−ジメチルホルムアミドが低温域に移送され、窒素原子含有のカーボンナノチューブが得られなくなるため好ましくなく、１００ｍｌ／ｍｉｎよりも流量が少ないと窒素原子含有カーボンナノチューブの収量が低下するため好ましくない。 The inert gas has a role as a carrier gas, and the flow rate is preferably in the range of 100 to 500 ml / min. If the flow rate of the inert gas is higher than 500 ml / min, undecomposed N, N-dimethylformamide is transferred to a low temperature region, and nitrogen atom-containing carbon nanotubes cannot be obtained. If the amount is too small, the yield of the carbon atom-containing carbon nanotubes decreases, which is not preferable.
不活性ガスはアルゴンが好適に考慮されるが、それ以外では、ヘリウム、ネオン等の希ガスを例示することができる。 Argon is preferably considered as the inert gas, but other than that, a rare gas such as helium or neon can be exemplified.
上記の操作と同時に、アンモニアガスを１００〜５００ｍｌ／ｍｉｎの流量で流すことが考慮される。アンモニアガスの流量が５００ｍｌ／ｍｉｎよりも多いとＮ，Ｎ−ジメチルホルムアミドが分解せずに逸散するため好ましくなく、１００ｍｌ／ｍｉｎよりも少ないとＮ，Ｎ−ジメチルホルムアミドの分解が十分に進行しないため好ましくない。 It is considered that ammonia gas is allowed to flow at a flow rate of 100 to 500 ml / min simultaneously with the above operation. If the flow rate of ammonia gas is higher than 500 ml / min, N, N-dimethylformamide will dissipate without being decomposed, which is not preferable. If it is lower than 100 ml / min, decomposition of N, N-dimethylformamide will not proceed sufficiently. Therefore, it is not preferable.
この後、シリコン基板は５００℃以上の温度で加熱され、６００℃〜９００℃が好適な範囲として考慮される。加熱温度が９００℃よりも高いと炭素−窒素の結合が切断されて、カーボンナノチューブ中の窒素原子の含有量が減少するため好ましくなく、５００℃よ
りも低いと、ナノチューブの成長が難しくなるため好ましくない。
Thereafter, the silicon substrate is heated at a temperature of 500 ° C. or higher, and 600 ° C. to 900 ° C. is considered as a suitable range. When the heating temperature is higher than 900 ° C., the carbon-nitrogen bond is broken, and the content of nitrogen atoms in the carbon nanotube is decreased. This is not preferable, and when the heating temperature is lower than 500 ° C., it is difficult to grow the nanotube. Absent.
加熱時間は、１０〜６０分が好適な範囲として考慮される。６０分より時間をかけると生成物が活性な基板の表面を覆ってしまい、ナノチューブの成長は進まない。また、１０分より短い時間では収量が低下してしまうため好ましくない。 10-60 minutes is considered as a suitable range for the heating time. When the time is longer than 60 minutes, the product covers the surface of the active substrate, and the growth of the nanotube does not proceed. Also, a time shorter than 10 minutes is not preferable because the yield decreases.
上記の操作終了後、シリコン基板表面に高窒素原子含有カーボンナノチューブが堆積する。 After completion of the above operation, high nitrogen atom-containing carbon nanotubes are deposited on the surface of the silicon substrate.
以下の実施例により、この出願の発明をさらに詳細に説明するが、この出願の発明はこれらに限定されるものではない。 The invention of this application will be described in more detail by the following examples, but the invention of this application is not limited thereto.
窒素雰囲気中で、４１ｍｌの関東化学（株）製のイソプロピルアルコール（純度９９．９％）と１ｍｌの関東化学（株）製のアセチルアセトン（純度９９．５％）の中に、５ｍｌの関東化学（株）製のアルミニウムトリ−ｓｅｃ−ブトキサイド（純度９５％）を室温ではげしく攪拌しながら３０分かけて滴下した。この溶液に関東化学（株）製の硝酸第二鉄（純度９９．９％）水溶液（濃度0.1Ｍ）と関東化学（株）製の七モリブデン酸六アン
モニウム（純度９９．０％）水溶液（濃度０．１Ｍ）の混合溶液をゆっくり攪拌しながら約３ｍｌ滴下した。この溶液は数分でゲル化するので、ゲル化する前に直ちにｎ−型シリコン基板に２〜３滴を滴下してスピンコートした。滴下後、数分で透明なゲル被膜になったので、このゲル化した薄膜のついたシリコン基板を２日間室温でエージングし、さらに、窒素ガス雰囲気中で１００℃に乾燥して、アルミナに酸化鉄と酸化モリブデンが保持された薄膜の付いたシリコン基板を得た。得られた薄膜付きシリコン基板を横型石英管状炉の中に設置した。一方、和光純薬工業（株）製のＮ，Ｎ−ジメチルホルムアミド（純度９９．５％）１８ｇを６０℃に加熱し、この液体中にアルゴンガスを３００ｍｌ／ｍｉｎの流量で吹き込んで霧状にして横型石英管状炉の中へ導入した。これと並行して乾燥アンモニアガスを２００ｍｌ／ｍｉｎの流量で横型石英管状炉の中へ移送した。シリコン基板を８００℃に加熱して、この温度で３０分間維持した。シリコン基板の表面に厚さ約１μｍの黒色の薄膜が堆積した。
In a nitrogen atmosphere, 5 ml of Kanto Chemical (purity 99.9%) in 1 ml of isopropyl alcohol (purity 99.9%) manufactured by Kanto Chemical Co., Ltd. and 1 ml of acetylacetone (purity 99.5%) manufactured by Kanto Chemical Co., Ltd. Aluminum tri-sec-butoxide (purity: 95%) manufactured by Kogyo Co., Ltd. was added dropwise over 30 minutes while stirring vigorously at room temperature. An aqueous solution of ferric nitrate (purity 99.9%) manufactured by Kanto Chemical Co., Ltd. (concentration 0.1 M) and an aqueous solution of hexaammonium heptamolybdate (purity 99.0%) manufactured by Kanto Chemical Co., Ltd. (concentration) About 3 ml of a mixed solution of 0.1M) was added dropwise with slow stirring. Since this solution gelled in a few minutes, 2 to 3 drops were immediately dropped onto the n-type silicon substrate and spin-coated before gelling. Since a transparent gel film was formed within a few minutes after the dropping, the silicon substrate with the gelled thin film was aged at room temperature for 2 days, and further dried at 100 ° C. in a nitrogen gas atmosphere to oxidize to alumina. A silicon substrate with a thin film holding iron and molybdenum oxide was obtained. The obtained silicon substrate with a thin film was placed in a horizontal quartz tubular furnace. On the other hand, 18 g of N, N-dimethylformamide (purity 99.5%) manufactured by Wako Pure Chemical Industries, Ltd. was heated to 60 ° C., and argon gas was blown into the liquid at a flow rate of 300 ml / min to form a mist. And introduced into a horizontal quartz tube furnace. In parallel with this, dry ammonia gas was transferred into a horizontal quartz tubular furnace at a flow rate of 200 ml / min. The silicon substrate was heated to 800 ° C. and maintained at this temperature for 30 minutes. A black thin film having a thickness of about 1 μm was deposited on the surface of the silicon substrate.
図１に、シリコン基板上に形成された黒色生成物の低倍率走査型電子顕微鏡像の写真を示した。 FIG. 1 shows a photograph of a low-magnification scanning electron microscope image of a black product formed on a silicon substrate.
この生成物は多くの亀裂の入った小片からなり、挿入図の高倍率走査型電子顕微鏡像の写真から分かるように、基板に垂直に密に配向した繊維状物であることが確認できた。 This product consisted of many cracked pieces, and as can be seen from the photograph of the high-magnification scanning electron microscope image in the inset, it was confirmed that the product was a fibrous material that was closely oriented perpendicular to the substrate.
図２に、黒色生成物の電子エネルギー損失スペクトルと挿入図にその低倍率透過型電子顕微鏡像を示した。 FIG. 2 shows the electron energy loss spectrum of the black product and the low magnification transmission electron microscope image in the inset.
挿入図の写真から繊維状物の直径は数ナノメートルから５０ナノメートルの範囲にわたっていることが確認できた。電子エネルギー損失スペクトルの結果から窒素原子と炭素原子の原子比は０．１９〜０．２５であることが分かり、従来から知られている窒素原子含有カーボンナノチューブに比べて窒素原子の含有量が高いことが確認できた。 From the photograph of the inset, it was confirmed that the diameter of the fibrous material ranged from several nanometers to 50 nanometers. As a result of the electron energy loss spectrum, it is understood that the atomic ratio of nitrogen atoms to carbon atoms is 0.19 to 0.25, and the content of nitrogen atoms is higher than that of conventionally known nitrogen atom-containing carbon nanotubes. I was able to confirm.
図３に、本発明で得られた高窒素原子含有のカーボンナノチューブの電界放出特性を測定した結果を示した。 FIG. 3 shows the results of measuring the field emission characteristics of the carbon nanotubes containing high nitrogen atoms obtained in the present invention.
この図は、試料と陽極間の距離を５０μｍずつ増加させて、電流と電圧の関係を調べたものであるが、０．０１ｍＡ／ｃｍ2の電流が流れるときの電圧を開始電圧とすると、開
始電圧の値は１．３２±０．２９Ｖ／μｍであり、１．８Ｖ／μｍにおける電流密度は８０μＡ／ｃｍ2であり、従来から知られているカーボンナノチューブや低窒素原子含有の
カーボンナノチューブと比べて低い開始電圧と高い放射電流密度を示すことが確認できた。
In this figure, the distance between the sample and the anode is increased by 50 μm, and the relationship between the current and the voltage is examined. If the voltage when the current of 0.01 mA / cm 2 flows is the start voltage, the start The voltage value is 1.32 ± 0.29 V / μm, and the current density at 1.8 V / μm is 80 μA / cm 2, which is compared with the conventionally known carbon nanotubes and carbon nanotubes containing low nitrogen atoms. It was confirmed that the low starting voltage and high radiation current density were exhibited.
以上詳しく説明した通り、この出願の発明によって、高い窒素原子含有量のカーボンナノチューブの製造方法が提供される。これによって、電界放出特性、ガス貯蔵特性、電子移動特性などに優れた特性を持った高い窒素原子含有量のカーボンナノチューブを得ることができ、電気部品の素材をはじめ、各種分野でその応用が期待でき、産業上においても有効に活用することができる。 As described in detail above, the invention of this application provides a method for producing carbon nanotubes having a high nitrogen atom content. This makes it possible to obtain carbon nanotubes with a high nitrogen atom content with excellent field emission characteristics, gas storage characteristics, electron transfer characteristics, etc., and are expected to be applied in various fields including electrical component materials. It can be used effectively in industry.
Claims (3)
ることを特徴とする窒素原子が結合したカーボンナノチューブの製造方法。 A nitrogen substrate characterized in that an alumina substrate holding iron oxide and molybdenum oxide is placed in a heating furnace, N, N-dimethylformamide vapor and ammonia gas are introduced into the furnace and heated at a temperature of 500 ° C. or higher. A method for producing carbon nanotubes bonded with atoms.
The method according to claim 1 or 2, wherein heating is performed in a temperature range of 600 ° C to 900 ° C.
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